Abstract
Abstract2‐Phenylselenomethyl‐1H‐benzimidazole (psbi) can form complexes in 2:1 ratio with coinage metal ions. Crystal structure analysis revealed a flattened metal coordination for [AgI(psbi)2](BF4) (1), approaching a distorted‐planar arrangement with weak Ag–Se bonds (d > 2.9 Å) and confirmed as energy minimum by DFT calculations. The typical Jahn–Teller system [CuII(psbi)2Cl2] (2) exhibits a planar CuN2Cl2 core with weak Se···Cu···Se axial ligation [3.2944(8) Å Cu···Se distance]. The oxygen‐sensitive compound [CuI(psbi)2](BF4) (3) exhibits electrochemically reversible oxidation in contrast to the silver(I) analogue 1.
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